Process for breaking petroleum emulsions



Patented May 25,1954

PROCESS FOR BREAKING PETROLEUM EMULSIONS Melvin De Groote, University City, Mo., assignor to Petrolite Corporation, Wilmington, Del., a

corporation of Delaware N Drawing. Application June 27, 1952, Serial No. 296,086

12 Claims.

This invention relates to processes or procedures particularly adapted for preventing,

breaking, or resolving emulsions of the waterin-oil type, and particularly petroleum emulsions.

The present invention is a continuation-inpart of my copending application, Serial No. 288,745, filed May 19, 1952.

My invention provides an economical and rapid process for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as roily oil, cut oil, emulsified oil,

etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

It also provides an economical and rapid process for separating emulsions which have been prepared under controlled conditions from min eral oil, such as crude oil and relatively soft waters or weak brines. Controlled emulsification and subsequent demulsification under the conditions just mentioned are of significant value in removing impurities, particularly inorganic salts, from pipeline oil.

The demulsifying agents employed in the present' demulsifying process are the products obtained by the process of condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, lowstage phenolaldehyde resin of the type described hereinafter as component (a) in Part 1; (b) a basic hydroxylated polyamine of the type described hereinafter as component (b) in Part 1, and (0) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible.

As far as the use of the herein described products goes for purpose of resolution of petroleum emulsions of the water-in-oil type, I particularly prefer to use those which as such or in the form of the free base or hydrate, i. e., in combination with water or particularly in the form of a salt of a low molal organic acid such as the acetate or hydroxy acetate, have sufiiciently hydrophile character to at least meet the test set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the various condensation products as such or in the form of the free base or in the form of the acetate, may not necessarily be xylene-soluble although they are in many instances. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a water-soluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

Reference is again made to U. S. Patent 2,499,- 368 dated March 7, 1950, to De Groote and Keiser. In said immediately aforementioned patent the following test appears:

The same is true in regard to the oxyalkylated resins herein specified, particularly in the lower stage of oxyalkylation, the so-called sub-surface-active stage. The surface-active properties are readily demonstrated by producing a xylene-water emulsion. A suitable procedure is as follows: in an equal weight of xylene. Such 50-50 solution is then mixed with 1-3 volumes of water and shaken to produce an emulsion. The amount of xylene is invariably sufficient to reduce even a tacky resinous product to a solution which is readily dispersible. The emulsions so produced are usually xylene-in-water emulsions (oil-inwater type) particularly when the amount of distilled water used is at least slightly in excess of the volume of xylene solution and also if shaken vigorously. At times, particularly in the lowest stage of oxyalkylation, one may obtain a water-in-xylene emulsion (water-in-oil type) which is apt to reverse on more vigorous shaking and further dilution with water.

If in doubt as to this property, comparison with a resin obtained from para-tertiary butylphenol and formaldehyde (ratio 1 part phenol to 1.1 formaldehyde) usingan acid catalyst and then followed by oxyalkylation using 2 moles of ethylene oxide for each phenolic hydroxyl, is helpful. Such resin prior to oxyalkylation has a molecular weight indicating about 4 units per resin molecule. Such resin, when diluted with an equal weight of xylene, will serve to illustrate the above emulsification test.

In a few instances, the resin may not be sufficiently soluble in xylene alone but may require Such The oxyalkylated resin is dissolved l such as xylene. It is to be the addition of some ethylene glycol diethylether as described elsewhere. It is understood that such mixture, or any other similar mixture, is considered the equivalent of Xylene for the purpose of this test.

In many cases, there is no doubt as to the presence or absence of hydrophile or surfaceactive characteristics in the products used in accordance with this invention. They dissolve or disperse in water; and such dispersions foam readily. with borderline cases, i. e., those which show only incipient hydro'phile or surface-active property (sub-surface-activity) tests for emulsifying properties or self-dispersibility are useful. The fact that a reagent is capable of pro ducing a dispersion in water is proof that. it is distinctly hydrophile. In doubtful cases, comparison can be made with the butylphenol-formaldehyde resin analog wherein 2 moles of ethylene oxide have been introduced for each phenolic nucleus.

The presenc of xylene or an equivalent water-insoluble solvent may mask the point at which a solvent-free product on mere dilution in a test tube exhibits self-emulsification. For this reason, if it is desirable to determine the approximate point where self-emulsification begins, then it is better to eliminate the xylene or equivalent from a small portion of the reaction mixture and test such portion. In some cases, such xylene-free resultant may show initial or incipient hydrophile properties, whereas in presence of xylene such properties would not be noted. In other cases, the first objective indication of hydrophile properties may be the capacity of the material to emulsify an insoluble solvent emphasized that hydrcphile properties herein referred to are such as those exhibited by incipient self-emulsification or the presence of emulsifying properties and go through the range of homogeneous dipersibility or admixture with water even in presence of added water-insoluble solvent and minor proportions of common electrolytes as occur in oil field brines.

Elsewhere, it is pointed out that an emulsification test may be used to determine ranges of surface-activity and that such emulsification tests employ a xylene solution. Stated another way, it is really immaterial whether a xylene solution produces a sol or whether it merely produces an emulsion.

For convenience, what is said hereinafter will be divided into five parts:

Part 1 is the introductory part as far as the demulsifying agents themselves are concerned, i. e., the amine-modified resins;

Part 2 is concerned with the general structure of the amine-modified resin and also the resin itself, which is used as a raw material;

Part 3 is concerned with appropriate basic hydroxylated polyamines which may be employed in the preparation of the herein described aminemodified resins;

Part 4 is concerned with the reactions involving the resin, the amine, and formaldehyde to produce the specific products or compounds; and

Part 5 is concerned with the use of the oilmodified resins obtained as described in Part 4 for the resolution of emulsions of the water-inoil, type.

PART 1 As previously stated, this invention is con-- Another aspect of the cerned with the use of demulsifiers for resolution or breaking of petroleum emulsions of the waterin-oil type of certain amine-modified resins. Such amine-modified resins have been described in the aforementioned co-pending application, Serial No. 288,745, filed May 19, 1952.

The demulsifying agents are heat-stable oxyalkylation-susceptible resinous condensation products of (a) a defined phenol-aldehyde resin, (1)) a defined basic hydroxylated polyamine, and (0) formaldehyde. The condensation reaction is conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and the resultants of reaction. invention, of course, is the procedure such condensation products.

The phenol-aldehyde resin designated as component (a) is an oxyalkylation-susceptible, fusible, nonoxygenated organic solventsoluble., water-insoluble, low stage phenolaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule. The phenol-aldehyde resin is difunctional only in regard to methylol-forming reactivity, and the resin is derived by reaction between a difunctional monohydricphenol and an aldehyde having not over 8 carbon atoms and. reactive toward the phenol. Also, the resin is formed in the substantial absence of trifunctional phenols. The phenol constituent of the resin is of the formula:

for making in which R is an aliphatic hydrocarbon radical having at least 4 carbon atoms and not more than 24- carbon atoms, and substituted in the. 2,4,6-position.

The basic hydroxylated polyamine designated as component (b) has at least one secondary amino, group andnot over 32 carbon atoms in any radical attached to. any amino nitrogen atom. Also, the polyamine is free from any primary amino radical, any substituted imidazoline radical and any substituted tetrahydropyrimidine radical.

This. invention in a more limited aspect relates to the. use as demulsifiers of certain polyaminemodified thermoplastic phenolaldehyde resins. For purpose of simplicity the invention, as far as demulsification is concerned, may be typified by reference to the resinous materials themselves. These resins may be exemplified by an idealized formula which may, in part, be an oversimplification in an efiort to present certain resin structure. Such formula would be the following:

in. which R represents an aliphatic hydrocarbon substituent generally having four and not over 18 carbon atoms but most preferably not over 14 carbon atoms, and n generally is a small whole number varying from 1 to 4. In the resin structure it. is. shown as being derived from formaldehyde. although obviously other aldehydes are equally satisfactory. The. amine residue in the above structure is derived from a hydroxylated may be indicated thus in which R represents any appropriate hydrocarbon radical, such as an alkyl, alicyclic, arylalkyl radical, etc., with the proviso that at least one occurrence of R contains an amino radical which is not part of a primary amino radical or part of a, substituted imidazoline radical or part of a substituted tetrahydropyrimidine radical, and with the further proviso that there be present at least one hydroxylated hydrocarbon radical such as a hydroxyl alkyl radicaLa hydroxy alicyclic radical, a cal, etc. Such hydroxylated radical need not be limited to a single hydroxyl group as in the case of an alkanol radical but may include 2 or more hydroxyl groups, such as a glycerol derivative or, in essence, a dihydroxy p-ropyl group.

Actually, what has been depicted in the formula above is only an over-simplified exemplification of that part of the polyamine which has the reactive secondary amino group. Actually, a more complete illustration is obtained by reference to oxyalkylated derivatives obtained by the oxyethylation or oxypropylation, for example, of substituted polyalkylene amines of the following structure:

in which R has its prior significance, R represents a hydrogen atom or radical R, D is a hydrogen atom or an alkyl group, n represents the numerals l to 10, and ac represents a small whole number varying from 1 to 7 but generally from 1 to 3, with the proviso that the other previously stated requirements are met. See U. S. Patent No. 2,250,176 dated July 22, 1941, to Blair. Reaction with an alkylene oxide, such as ethylene oxide or propylene oxide must of course be sure that the derivative so obtained still has at least one secondary amino hydrogen group, all of which will be illustrated by numerous examples subsequently.

See also U. S. Patent No. 2,362,464, dated November 14, 1944, to Britton et al., which describes alkylene diamines and polymethylene diamines having the formula NCHzCnH2nN H \H where R represents an alkyl, alkenyl, cycloalkyl, or aralkyl radical, and n represents a comparatively small integer such as 1 to 8. Such compound as the one just described can be reacted with a single mole of ethylene oxide or propylene oxide or glycide to give a suitable reactant.

A further limitation in light of the required basicity is that the secondary amino ralical shall not be directly joined to an aryl radical or acyl radical or some other negative radical. Needless to say, what has been stated above in regard to the groups attached to nitrogen is not intended to exclude an oxygen-interrupted carhydroxy alkylaryl radibon atom linkage or a ring linkage as in the in stance of compounds obtained by converting an N-aminoalkylmorpholine of the formula OHz-CH2 wherein N is a whole number from 2 to 12 inclusive, and the nitrogen atoms are separated by at least two carbon atoms, intoa secondary amine by means of an alkylene oxide, such as ethylene oxide, propylene oxide, or glycide, so as to yield a compound such as The introduction of two such hydroxylated polyamine radicals into a comparatively small resin molecule, for instance, one having 3 to 6 phenolic nuclei as specified, alters the product in a number of ways. In the first place, a basic nitrogen atom, of course, adds a hydrophile effect; in the second place, depending on the size of the radical R, there may be a counter-balancing hydrophobe effect or one in which the hydrophobe efiect more than counterbalances the hydrophile effect of the nitrogen atom. Finally, in such cases where R contains one or more oxygen atoms, another effect is introduced, particularly another hydrophile effect. In the present procedure the polyamino reactant invariably has at least one hydroxyl group and also may have a reoccurring ether linkage, all of which in turn affects the hydrophile properties.

Combinations, resinous or otherwise, have been prepared from phenols, aldehydes, and reactive amines, particularly amines having secondary amine groups. Generally speaking, such materials have fallen into three classes; the first represents non-resinous combinations derived from phenols as such; the second class represents resins which are usually insoluble and used for the purpose for which ordinary resins, particularly thermo-setting resins are adapted. The third class represents resins which are soluble as initially prepared but are not heat-stable, i. e., they are heat-convertible, which means they are not particularly suited as raw materials for subsequent chemical reaction which requires temperatures above the boiling point of water or thereabouts.

The third class of material which of the three classes mentioned approaches the closest to the herein-described derivatives or resinous amino derivatives is described in U. S. Patent No. 2,031,557, dated February 18, 1936, to Bruson. The procedure described in said Bruson patent apparently is concerned with the use of monoamine only.

The resins employed as raw materials in the instant procedure are characterized by the presence of an aliphatic radical in the ortho or para position, i. e., the phenols themselves are difunctional phenols. This is a difierentiation from the resins described in the aforementioned Bruson Patent No. 2,031,557, insofar that said patent discloses suitable resins obtained from metasubstituted phenols, hydroxybenzene, resorcinol, p,p(dihydroxydiphenyl) dimethylmethane, and the like, all of which have at least three points of reaction, per phenolic nuclei and as a result can yield resins which may be at least incipiently cross-linked even though they areappa'rently still soluble in oxygenated organic solvent or else are employed, onemay obtainzcross-linking which indicates that one or more of the phenolic nuclei have been converted from a difunctional radical to a trifunctional radical, or in terms of the resin, the molecule as a whole has a methylol-forming reactivity greater than 2. Such shift can take place after the resin has been formed or during resin formation. Briefly, an example is simply where an alkyl radical, such as methyl, ethyl, propyl, butyl, or the like, 'shifts from. an ortho position to a meta position, or. from a para position to a meta position. For instance, in. the case-of phenol-aldehyde varnish resins, one .can prepare at least some in which the resins, instead of having only two points of reaction can have three, and possibly more points of reaction,

with .formaldehyde, or any other reactant which tends to form a methylol or substituted methylol group.

Apparently there. is no similar limitation in regard to the resins employed in the aforementionedBruson Patent 2,031,557, for the reason that one may prepare suitable resins from phenols of the kind already specified which invariably and inevitably would yield a resin having a functionality greater than two in the ultimate resin molecule.

"The resins herein employed are soluble in a non-oxygenated hydrocarbon solvent, such as benzene .or. Xylene. As pointed outin the aforementioned Bruson Patent 2,031,557, one of the objectives isto convert the phenol-aldehyde resins employed as raw materials in such a way as to render them hydrocarbon soluble, i. e., soluble in benzene. The original resins of U. S. Patent 2,031,557,.are selected. on. the basis. of solubility in an oxygenated inert organic solvent, such as alcohol or dioxane. It is immaterial whether the resins here employed are .soluble in dioxane or alcohol, but they must be soluble in benzene.

The resins herein employed as raw materials must be comparatively low molal products having on the average 3 to 6 nuclei perresin molecules. The resins employed in the aforementioned U. S. Patent No. 2,031,557, apparently. needv not meet any such limitations.

The condensation products here obtained,

whether in theform of..the free base orthe salt, donot go over to .theinsoluble stage Qnheating. Thisapparently. is..not .true. of. the .materials described in aforementioned Bruson Patent 1 2,031,557 and apparentlyone-of the-objectives with which the invention is concerned, is .to obtain a heat-convertible condensation product. The condensation product obtained according to the present invention. isheat stable and,-in fact,

one of its outstanding qualities is that it can be subjected to oxyalkylation, particularly oxyethylation or oxypropylation, under conventional conditions, i. e., presence of an alkaline catalyst, for example, but in any event at a temperature above 100 C. without becoming an insoluble mass.

Although these condensation" products have been prepared primarily with the thought in mindlthat they are precursors" for subsequent reaction, yet assuoh and without further reaction, they have definitely valuable properties-and uses as hereinafter pointed out.

' What has been'said previously inregard toheat stability, particularly when employedas a reactant for preparation of derivatives, :is stillri-rhportant from the standpoint-ormanufacturesof the condensation products themselves insofar that in the condensation process employed in preparing the compounds described subsequently in detail, there is no objection to the employing ofa temperature above the boiling point of-water. As a matter of fact, all theexamples. included subsequently employ temperatures going up-to 140 to 150 C. If. one wereusingresinsofithe kinddescribed in U. S. Patent No. 2,031,557wit appears desirable and perhaps absolutely necese sary that the temperature be kept relatively low, for instance, between C. and 100 C... and more specifically at a temperature of 80". to 90 0. There is no such limitation in the condensation procedure herein described-for reasonswhich .are obvious in. light of What has been saidpreviously.

What is said above deserves further amplification at this point for the reason that it. may shorten what is said subsequently'in regard to the production of the herein described condensation products. As pointed out in the instant invention the resin selected is xylene or benzene soluble, which differentiates the-resins from those employed in the aforementioned Bruson Patent No. 2,031,557. Since formaldehyde generally-is employed economically in an aqueous phase to 40% solution, for example) it-is necessary to have manufacturing-procedurewhich will allow reactions to take place at the interfaceofithe two immiscible liquids, to wit, the formaldehyde solution and the resin solution, on the assumption that generally the amine willdissolve in one phase or the other. Although reactions of the kind herein described will begin at least. at comparativelylow temperatures, for instance, 30C., 40 C., or C.,v yet the reaction does not go to completion except by the use of the higher temperatures. The use of higher temperatures means, of course, that'the condensation product obtained at the end of the reaction must not be heat-reactive. Of course, one. can add an. oxygenated solvent such as alcohol, dioxane, various ethers of glycols, or the like, and produce a. homogeneous phase. If this latter procedure .is employed in, preparing the herein described condensations it is purely a matter of. convenience, but whether it is or not, ultimately the temperature must still pass within the zone indicated elsewhere, i. e., somewhere above the boiling point of water unless some obvious equivalent procedure is used.

Any reference, as in the hereto appended claims, to the procedure employed in the process is not intended to limit the method or order in which the reactants are added, commingled or reacted. The procedure has been referred to as a condensation process for obvious reasons. As pointed out elsewhere it is my preference to dissolvethe resin in a suitable solvent, add the amine, and then add the formaldehyde as a 37% solution. However, all three reactants can be added in any order. I am inclined to believe that in the presence of a basic catalyst, such as the amine employed, that the formaldehyde produces methylol groups attached to the phenolic nuclei which, in turn, react with the amine. It would be immaterial, of course, if the formaldehyde reacted with the amine so as to introduce a methylol group attached to nitrogen which, in turn, would react with the resin molecule. Also, it would be immamoles of a basic nonhydroxylated secondary terial if both types of compounds were formed amine as specified, following the same idealized which reacted with each other with the evolution over-simplification previously referred to, the reof a mole of formaldehyde available for further sultant product might be illustrated thus:

reaction. Furthermore, a reaction could take place in which three different molecules are 0H H I OH simultaneously involved although, for theoretical reasons, that is less likely. Whatissaid herein in H H H H In the above formula n represents a small Whole 25 in the instance of low molecular weight polymers 30 this respect is simply by way of explanation to avoid any limitation in regard to the appended R R n R claims.

PART 2 The basic polyamine may be designated thus: It is well known that one can readily purchase H on the open market, or prepare, fusible, organic solvent-soluble, water-insoluble resin polymers of a composition approximatel in an id li form subJect to what has been said previously as to the by t f presence of at least one amine radical in at least one occurrence of R with the proviso, as pre- OH H OH viously stated, that the amine radical be other gthan a primary amine radical, a substituted imidazoline radical or a substituted tetrahydro- I pyrimidine radical, with the proviso that there R R n R must be present at least one hydroxyl radical as part of at least one of the occurrence of R. Hownumber Varying from 1 to 6, 7 or 8, or more, up ever, if one attempts to incorporate into the forto probably 10 or 12 units. particularly when the mula resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is a structure such as an oxyethylated or oxypropylated deviative of a substituted polyalkyleneamine of the following type:

where the total number of phenol nuclei varies from 3 to 6, i. e., n varies from 1 to 4; R represents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to 14 carbon atoms, N

such as a butyl, amyl, hexyl, decyl or dodecyl rad- -C..Hz...(o..Hi..N.D),N

ical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of in which the various characters have the-same course, be derived from any other reactive aldesignificance as in initial presentation of this hyde having 8 carbon atoms or less. formula, then one becomes involved in added dif- Because a resin is organic solvent-soluble does 40 ficulties in presenting an overall picture. Thus, n t me n it is n ss ril u le in ny organi for sake of simplicity, the hydroxylated polyamine solvent. This is particularly true where the resins will be depicted as are derived from trifunctional phenols as previously noted. However, even when obtained from a difunctional phenol, for instance para-phenyl p o y Obtain a resin which is I101? subject to the limitation and explanation preuble in anonoxygenated solvent, such as henviously noted, o 0 y t requires an Xygenated $01- In conducting reactions of this kind one does vent such as a l w m lal al h i xane, or dinot necessarily obtain a hundred per cent yield for ethylglycol dietliylether. Sometimes a mixture of v obvious reasons Certain side reactions may take the two solvents (oxygenated and nonoxygenated) p1a,ce F r instance, 2 mole f amine may comwill serve. See Example 9a of U. S. Patent No. bine ith one mole of the aldehyde, or only one dated M ch 7, 195 o De te d mole of the amine may combine with the resin Keiser. molecule, or even to a very slight extent, if at The resin herein employed as raw materials all, 2 resin units may combine without any amine must be soluble in a n n xyeen v n h in the reaction products, as indicated in the folas benzene or xylene. This presents no problem lowing formulas:

insofar that all that is required is to make a solu- R1\ H R. bility test on commercially available resins, or NCN else prepare resins which are xylene or benzene- R/ H R1 soluble as described in aforementioned U. S. Pat- OH OH OH ent No. 2,499,365. or in U. S. Patent No. 2,499,368 H I H dated March 7, 1950, to De Groote and Keiser. g g -g- In said patent there are described phenol-aldehyde resins of the type noted as component (a) in Part 1 above. R R n R n R n R R R n R If one selected a resin of the kind just described As has been pointed out previously, as far .as previously and reacted approximately one molev of the resin unit goes one can use a mole of aldehyde the resin with two moles of formaldehyde and two other than formaldehyde, such as acetaldehyde,

unitmay be exemplified thus:

in which R is the divalent radical obtained from the particular aldehyde-employed to form the resin. For reasons which are obvious the condensation product obtained .appears to be described best in terms of the method of manufacture. As previously stated the preparation of resins, the kind herein employed as reactants, is Well known. See. previously mentioned U. S." Patent 2,499,368. 'Resins can be made using an acid catalyst or. basic catalyst or a catalyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all. It'is preferable that the resins employed. be substantially neutral. In other wordsfif prepared by using a strong acid as a catalyst, suchstrong acid should be neutralized. "Simi1arly,"if a strong base is used as a catalyst itis preferable that the base be neutralized although I have found that sometimes the reaction described proceeded ,more rapidly in the presence of a small amount of a free" base. "The'a'mount may be as small as a 200th"of"aper'c'ent and" as much as a few lOths of a percent. Som'etnhes'inoderate' increase in caustic soda and caustic potash may be used.

However, the mostdesirable procedure in practically every' case is to have the resin neutral.

'In'preparingresinsone doesnot get a single polymer, i.:=e.,-'one':h'aving' just 3 units, or just 4 -units,'o1: just 5 units, or. just 6 units, etc. It "is usually-a-mixture; forinstance, one approximating 4'- phenolic nuclei will have some 'trimer and pentamer present. Thus, --'the molecular weight may be such that it corresponds to a fractional value for n as efor example, 3.5, 4.5 or 5.2.

"- In the-actual manufacture of the resins I'found" no reason for using other than thosawhiclr are 12 *PART'3 "has been pointed out, the amine herein employed as" a" reactant .is a hydroxylated. basic polyamine andpr'eferably a strongly basic poly- 5 amine having 'at least onesecond'ary amino radie21," free'fr'omp'riinary amino groups, free'from substituted imidazoline groups, and free from "substituted tetrahydrop'yr'imidine "groups, "in whicli'the hydrocarb'orrradicals' present,'whether moi'iovalent' or divalent are alkyl; alicyclicjarylalkyl, or heterocyclic in character, subject of course to the inclusionbf" a hydroxyl group at- -tached= to l a carbon atom which iri turn-is?v part 1V or a monovalent or. divalent radical.

Previous referencehas been'made to a number =-=o-polyamines whichare satisfactory for use .as reactants in the instant condensation procedure. They can be obtained by hydroxyalkylation of low cost polyamines. The cheapest amines available are polyethylene aminesand polypropylene amines. In the case of the polyethylene amines there may be as many as'5 6 or '7 nitrogen atoms. Such amines aresusceptible to terminal alkylation or-the equivalent, i. e., reactions which con- 115 vert the terminal primary amino group or groups into -.a secondaryor tertiary amine radical. In --.the case ofpolyamines having at least 3 nitrogen -.-atoms ormore, both terminal groups could be converted into tertiary groups, or one terminal 1., group could be converted into a tertiary group and theother into a secondary amine group. In the same way, the polyamines can be subjected to hydroxyalkylation by reaction with ethylene oxide, propylene oxide, glycide, etc. In some instances, depending onthestructure, both types of reaction may be employed, i. e., one type to introduce a hydroxy ethyl group, for example, and another type tointroducea methyl or ethyl radical. 40 Byway-of example the following formulas are included. It will be noted they include such polyamines which, instead of being obtained from ethylene dichloride; propylene dichloride, or the like,-'-areobtained from dichloroethyl ethers in which: the-divalent radical has a carbon atom -chaininterrupted by an oxygen atom:

lowest in -pr1ceand--most readily available 'com- CH3 mercially. 1 For purposes-of convenience suitable *NCZHiNCZHiN resmsare characterized mthe *followmgtable: H0 CzH/ H onLoH TABLE I 4 'Mol Wt Example R Position R derived n a of Resin Number of R from Molecule 992. 5 tertiary butyl 1""882. 5 secondary u yl 882. 5 cyclo-hexyl. 1, 025. 5 tertiary amyl 95915 Mixed secondary and 805. 5

tertiary amyl. propyl 8 05. 5 tertiary hexyl. I. l, 036. 5 octyl 1, 190. 5 nonyl. 1;267. 5 decyl al; 344. 5 dodecyl 1, 498. 5 13a tertiary buty l 945. 5 tertiary amy 1, 022. 5 nonyl 1, 330. 5 tertiary butyl 1, 071.5 tertiary amyl. 1, 148. 5 1, 456. s l, 008. 5

' caHs 02115 N 02BX21; C 2H4N HO C2134 oimoH HO C2114 HO 02H;

CH3 CH3 HO C2H4/ HOC2H4 Another procedure for producing suitable polyamines is a reaction involving first an alkylene imine, such as ethylene imine or propylene imine, followed by an alkylene oxide, such as ethylene oxide, propylene oxide or glycide.

What has been said previously may be illustrated by reactions involving a secondary alkyl amine, or a secondary aralkyl amine, or a secondary alicyclic amine, such as dibutylamine, dibenzylamine, dicyclohexylamine, or mixed amines with an imine so as to introduce a primary amino group which can be reacted with an alkylene oxide followed by reaction with an imine and then the use of an alkylene oxide again. Similarly, one can start with a primary amine and introduce two moles of an alkylene oxide so as to have a compound comparable to ethyl diethanolamine and react with two moles of an imine and then with two moles of ethylene oxide.

Reactions involving the same reactants previously described, i. e., a suitable secondary monoamine plus an alkylene imine plus an alkylene oxide, or a suitable monoamine plus an alkylene' oxide plus an alkylene imine and plus the second introduction of an alkylene oxide, can be applied to a variety of primary amines. In the case of primary amines one can either employ two moles of an alkylene oxide so as to convert both amino hydrogen atoms into an alkanol group, or the equivalent; or else the primary amine can be converted into a secondary amine by the alkylation reaction. In any event, one can obtain a series of primary amines and corresponding secondary amines which are characterized by the fact that such amines include groups having repetitious ether linkages and thus introduce a definite hydrophile efiect by virtue of the ether linkage. Suitable polyether amines susceptible to conversion in the manner described include those of the formula in which a: is a small or 12; n is an integer inclusive; m represents the numeral 1 to 2; and

m represents a number 0 to 1, with the proviso that the sum of m plus m equals 2; and R has its prior significance, particularly as a hydrocarbon radical.

The preparation of such amines has been described in the literature and particularly in two United States patents, to wit, U. S. Nos., 2,325,514, dated July 27, 1943, to Hester, and 2,355,337, dated August 8, 1944, to Spence. The latter patent describes typical haloalkyl ethers such as CHaOCzHlCI Such haloalkyl ethers can react with ammonia, or with a primary so obtained and suitable for conversion into ap-- propriate polyamines are exemplified by (CH3OCH2CH2CH2CH2CH2CH2) zNH Other similar secondary monoamines equally suitable for such conversion reactions in order to yield appropriate secondary amines, are those of the composition RO(CHz)a \NH R 0 om)/ as described in U. S. May 8, 1945, to Jones et al. R may be methyl, ethyl, propyl, amyl, octyl, etc.

Other suitable secondary converted into appropriate polyamines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of cyclohexylmethylamine or the alkylation of similar primary amines, or for that matter, amines of the kind described in U. S. Patent No. 2,482,- 546 dated September 20, 1949, to Kaszuba, provided there is no negative group or halogen attached to the phenolic nucleus. Examples include the following; beta-phenoxyethylamine, gammaphenoxypropylamine, beta-phenoxy-alpha-methylethylamine, and beta-phenoxypropylamine.

Other secondary monoamines suitable for conversion into polyamine. are the kind described in British Patent No. 456,517, and may be illustrated by In light of the various examples of polyaminesl which have been used for illustration it may be well to refer again to the fact that previously the amine was shown as RI HN whole number havingJa; value 01' 1 or more, and may be as much as 10': having a value 01 2 to 4,

amine such as methylamine, ethylamine, cyclohexylamine, etc., to produce a Patent No. 2,375,659 dated In the above formula.

amines which can be In the first of the two above formulas if the reaction involves a terminal amino hydrogen obviously the radicals attached to the nitrogen atom, which in turn combines with the methylene bridge, would be different than if the reaction took place at the intermediate secondary amino radical as differentiated from the terminal group. Again, referring to the second formula above, although a terminal amino radical is not involved it is obvious again that one could obtain two different structures for the radicals attached to the nitrogen atom united to the methylene bridge, depending on whether the reaction took place at either one of the two outer secondary amino groups, or at the central secondary amino group. If there are two points of reactivity towards formaldehyde as pies it is obvious that one might get a. mixture in which in part the reaction took place at one point and in part at another point. Indeed, there are well known suitable polyamine reactions where a large variety of compounds might be obtained due to such multiplicity of reactive radicals. This can be illustrated by the following formula:

Certain hydroxylated polyamines which may be employed and which illustrate the appropriate type of reactant used for the instant condensation reaction may be illustrated by the following additional examples:

aoomonzNa-on nocincnmn n2 illustrated by the above exam- 1 trated in an idealized simplication, toactually depict the final product of the ooor else from a As is well known one can prepare ether amino alcohols of the type PART FOUR The products obtained by the herein described processes represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illusit is difficult generic mixture except in itself.

Previous reference has been made to the fact that the procedure herein employed is comparable, in a general way, to that which corresponds to somewhat similar derivatives made either from phenols as dilferentiated from a resin, or in the manufacture of a phenol-amine-aldehyde resin; particularly selected resin and an amine and formaldehyde in the manner described in Bruson Patent No. 2,031,557 in order to obtain a heat-reactive resin. Since the condensation products obtained are not heat-convertible and since manufacture is not restricted to a single phase system, and since temperatures up to C. or thereabouts may be employed, it is obvious that the procedure becomes comparatively simple, Indeed, perhaps no description is necessary over and above what has been said previously, in light of subsequent examples. However, for purpose of clarity the following details are included.

A convenient piece of equipment for preparation of these cogeneric mixtures is a resin pot of the kind described in aforementioned. U. S. Patent No. 2,499,368. In most instances the resin selected is not apt to be a fusible liquid at the early or low temperature stage of reaction if employed as subsequently described; in fact, usually it is apt to be a solid at distinctly higher temperatures, for instance, ordinary room temperature.

terms of the process Thus, I have found it convenient td use a solvent and particularly one which can be removed readily at a comparatively moderate temperature, for instance, at 150 C. A suitable solventis usually benzene, xylene, or comparable petroleum hydrocarbon or a mixture of such or similar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures; containing such solvents are not here included as raw materials. The reaction can be conducted in such a way that the initial reaction, and perhaps the bulk of the reaction, takes place in polyphase system. However, if desirable, one can use an oxygenated solvent such as a lowboiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols can be used or one can use a comparatively non-volatile solvent such as dioxane or the diethylether of ethylene glycol. One can also use a mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not required in the sense that it is not necessary to use an initial resin which is soluble only in any oxygenated solvent as just noted, and it is not necessary to have a single phase system for reaction.

Actually, water is apt to be present as a solvent for the reason that in most cases aqueous formaldehyde is employed, which may be the commercial product which is approximate 37%, or it may be diluted down to about 30% formaldehyde. However, paraformaldehyde can be used but it is more difficult perhaps to add a solid material in stead of the liquid solution and, everything else being equal, the latter is apt to be more economical. In any event, water is present as water of reaction. If the solvent is completely removed at the end of the process, no problem is involved if the material is used for any subsequent reaction. However, if the reaction mass is going to be subjected to some further reaction where the solvent may be objectionable, as in the case of ethyl or hexyl alcohol, and if there is to be subsequent oxyalkylation, then, obviously, the alcohol should not be used or else it should be removed. The fact that an oxygenated solvent need not be employed, of course, is an advantage for reasons stated.

Another factor, as far as the selection of solvent goes, is whether or not the cogeneric mixture obtained at the end of the reaction is to be used as such or in the salt form. The ccgeneric mixtures obtained are apt to be solids or thick viscous liquids in which there is some change from the initial resin itself, particularly if some of the initial solvent is apt to remain without complete removal. Even if one starts with a resin which. is almost Water-white in color, the products obtained are almost invariably a red in color or at least a red-amber, or some color which includes both an amber component and a reddish component. By and large, the melting point is apt to be lower and the products may be more sticky and more tacky than the original resin itself. Depending on the resin selected and on the amine selected the condensation product or reaction mass on a solvent-free basis may be hard, resinous and comparable to the resin itself. The products obtained, depending on the rea-ctants selected, may be water-insoluble or we.-

ter-dispersible, or water-soluble, or close to being water-soluble. Water solubility is enhanced, of

course, by making a solution in the acidified vehicle such as a dilute solution, for instance, a

solution. of hydrochloric acid, acetic acid, hy-

droxyacetic acid, etc. One also may convert the finished product into salts by simply adding a stoichiometric amount of any selected acid and removing any water present by refluxing with benzene or the like. In fact, the selection of the solvent employed may depend in part whether or not the product at the completion of the reaction is to be converted into a salt form.

In the next succeeding paragraph it is pointed out that frequently it is convenient to eliminate all solvent, using a temperature of not over C. and employing vacuum, if required. This applies, course, only to those circumstances where it is desirable or necessary to remove the solvent. Petroleum solvents, aromatic solvents, etc, can be used. The selection of solvent, such as benzene, Xylene, or the like, depends primarily on cost, 1. e., the use of the most economical solvent and also on three other factors, two of which have been previously mentioned; (a) is the solvent to remain in the reaction mass without removal; (Z2) is the reaction mass to be subjected to further reaction in which the solvent, for instance, an alcohol, either low boiling or high boiling, might interfere as in the case of oxyalkylation; and the third factor is this, (0) is an effort to be made to purify the reaction mass by the usual procedure as, for example, a water-wash to remove the water-soluble unreacted formaldehyde, if any, or a water-wash to remove any unreacted water-soluble polyamine, if employed and present after reaction? Such procedures are well known and, needless to say, certain solvents are more suitable than others. Everything else being equal, I have found xylene the most satisfactory solvent.

I have found no particular advantage in using a low temperature in the early stage of the reaction because, and for reasons explained, this is not necessary although it does apply in some other procedures that, in a general way, bear some similarity to the present procedure. There is no objection, of course, to giving the reaction an opportunity to proceed as far as it will at some low temperature, for instance, 30 to 40 but ultimately one must employ the higher temperature in order to obtain products of the kind herein described. If a lower temperature reaction is used initially the period is not critical, in fact, it may be anything from a few hours up to 24 hours. I have not found any case where it was necessary or even desirable to hold the low temperature stage for more than 24 hours. In fact, I am not convinced there is any advantage in holding it at this stage for more than 3 or l hours at the most. This, again, is a matter of convenience largely for one reason. In heating and stirring the reaction mass there is a tendency for formaldehyde to be lost. Thus, if the reaction can be conducted at a lower temperature so as to use up part of the formaldehyde at such lower temperature, then the amount of unreacted formaldehyde is decreased subsequently and makes it easier to prevent any loss. Here, again, this lower temperature is not necessary by virtue of heat convertibility as previously referred to.

If solvents and reactants are selected so the reactants and products of reaction are mutually soluble, then agitation is required only to the extent that it helps cooling or helps distribution of the incoming formaldehyde. This mutual solubility is not necessary as previously pointed out but maybe convenient under certain circum stances. On the other hand, if the products are not mutually soluble then agitation should be more vigorous for the reason that reaction probably takes place principally at the interfaces and the more vigorous the agitation the more interfacial area. The general procedure employed is invariably the same when adding the resin and the selected solvent, such as benzene or xylene. Refluxing should be long enough to insure that the resin added, preferably in a powdered form, is completely soluble. However, if the resin is prepared as such it may be added in solution form, just as preparation is described in aforementioned U. S. Patent 2,499,368. After the resin is in complete solution the polyamine is added and stirred. Depending on the polyamine selected, it may or may not be soluble in the resin solution. If it is not soluble in the resin solution it may be soluble in the aqueous formaldehyde solution. If so, the resin then will dissolve in the formaldehyde solution as added, and if not, it is even possible that the initial reaction mass could be a three-phase system instead of a two-phase system although this would be extremely unusual. This solution, or mechanical mixture, if not completely soluble is cooled to at least the reaction temperature or somewhat below, for example 35 C. or slightly lower, provided this initial low temperature stage is employed. The formaldehyde is then added in a suitable form. For reasons pointed out I prefer to use a solution and whether to use a commercial 37% concentration is simply a matter of choice. In large scale manufacturing there may be some advantage in using a 30% solution of formaldehyde but apparently this is not true on a small laboratory scale or pilot plant scale. 30% forma1dehyde may tend to decrease any formaldehyde loss or make it easier to control unreacted formaldehyde loss.

On a large scale if there is any difliculty with formaldehyde loss control, one can use a more dilute form of formaldhyde, for instance, a 30% solution. The reaction can be conducted in an autoclave and no attempt made to remove water until the reaction is over. Generally speaking, such a procedure is much less satisfactory for a number of reasons. For example, the reaction does not seem to go to completion, foaming takes place, and other mechanical or chemical difliculties are involved. I have found no advantage in using solid formaldehyde because even here water of reaction is formed.

Returning again to the preferred method of reaction and particularly from the standpoint of laboratory procedure employing a glass resin pot, when the reaction has proceeded as one can reasonably expect at a low temperature, for instance, after holding the reaction mass with or without stirring, depending on whether or not it is homogeneous, at 30 or 40 C. for 4 or 5 hours, or at the most, up to -24 hours, I then complete the reaction by raising the temperature up to 150 C., or thereabouts as required. The initial low temperature procedure can be eliminated or reduced to merely the shortest period of time which avoids loss of polyamine or formaldehyde. At a higher temperature I use a phase-separating trap and subject the mixture to reflux condensation until the water of reaction and the water of solution of the formaldehyde is eliminated. I then permit the temperature to rise to somewhere about 10 C., and generally slightly above 100 C., and below 150 C. by eliminating the solvent or part of the solvent so the reaction mass stays within this predetermined range. This period of heating and refluxing, after the water is eliminated, is

continued until the reaction mass is homogeneous and then for one to three hours longer. The removal of the solvents is conducted in a conventional manner in the same way as the removal of solvents in resin manfacture as described in aforementioned U. S. Patent No. 2,49 ,368.

Needless to say, as far as the ratio of reactants goes I have invariably employed approximately one mole of the resin based on the molecular weight of the resin molecule, 2 moles of the secondary polyamine and 2 moles of formaldehyde. In some instances I have added a trace of caustic as an added catalyst but have found no particular advantage in this. In other cases I have used a slight excess of formaldehyde and, again, have not found any particular advantage in this. In other cases I have used a slight excess of amine and, again, have not found any particular advantage in so doing. Whenever feasible I have checked the completeness of reaction in the usual ways, including the amount of water of reaction, molecular weight, and particularly in some instances have checked whether or not the endproduct showed surface-activity, particularly in a dilute acetic acid solution. The nitrogen content after removal of unreacted polyamine, if any is present, is another index.

In the hereto attached claims reference is made to the product as such, 1. e., the anhydro base. Needless to say, the hydrated base, i. e., the material as it combines with water or the salt form, with a combination of suitable acids as noted, is essentially the same material but is merely another form and, thus, the claims are intended to cover all three forms, 1. e., the anhydro base, the free base, and the salts.

In light of what has been said previously, little more need be said as to the actual procedure employed for the preparation of the herein described condensation products. The following example will serve by way of illustration:

Example 11) The phenol-aldehyde resin is the one that has been identified previously as Example 2:1. It was obtained from a partertiary butyl phenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3 phenolic nuclei, as the value for n which excludes the 2 external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei excluding the 2 external nuclei, or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color.

882 grams of the resin identified as 2a preceding, were powdered and mixed with a considerably lesser weight of xylene, to wit, 500 grams. The mixture was refluxed until solution was complete. It was then adjusted to approximately 33 to 38 C., and 296 grams of symmetrical di(hydroxyethyl)ethylenediamine were added. The mixture was stirred vigorously and formaldehyde used was a 30% solution and the amount employed was 200 grams. It was added in a little over 3 hours. The mixture was stirred vigorously and kept within a temperature range of 33 to 48 C. for about 17 hours. At the end of this time it was refluxed using a phase-separating trap and a small amount of aqueous distillate withdrawn from time to time. The presence of formaldehyde was noted. Any unreacted formaldehyde seemed to disappear within about 3 hours or thereabouts, ,As soon as the odor of formaldeh-yd'e was nolonger particularly noticeableor detectible the phase-separating trap was set. so as toeliminate all the water of solution and rear:- tion.

perature reached approximately 150 haps a little higher. kept at this temperature for a little over 4 hours and the reaction stopped. During this time material was dark red in color and had the eonsistency' of a sticky fluid or tacky resin. .The overall time for reaction: was somewhat under 80 hours. In other examples it varied from 24 tomore than 36 hours. The time can be reduced by cutting the low temperature period to approximate1-y'3 to 6 hours. Note that in Table II following there are a large number of added examples illustrating the same procedure. In each case the initial mixture was stirred and held at a fairly low temperature (30 to 40 C'.) for a period of several hours. Then refluxing was employed until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phase-separating trap was employed to separate out all the water, both the solution and condensation. After all the water had been separated enough xylene was taken out to have the final product reflux for several hours somewhere in the range of 145 to 150 0., or thereabouts.v Usually the mixture yielded a clear solution by the time the bulk of the water, or all of the water, had been removed.

Note that as pointed out previously, this procedure is illustrated by 24 examples in Table II.

TABLE Ii After the water was eliminated part. of the xylene was removed until the tem- C.- or per-- The reaction masswas no emeamrkem Amine I ereNnoiH onmnem ocmon I ornNn-ora 7 PART 5 Conventional demul'siiying agents employed inthe treatment of oil field" emulsions are usedas such, or after dilution with any suitable solvent, such as water, petroleum hydrocarbons; such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc: Alcohols, particularly aliphatic alcohols, such asmethyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alco- Strength of Formaldehyde Soln. and Amt.

Amine Used and Resin Amt,

' mount Used gis.

Amine A, 296 g l- Amine A, 148 g As to the formulas of the above amines re-' ferred to as Amine A through Ami e I, inclusive, see immediately" following:

Solvent Used.

. Xylene, 500g;

O leum, etc.,. may be employed as diluents.

demulsifying agents.

and Amt.

ylene, 625 g. ylen 315 g 23 other suitable well-known classes of demulsifying agents.

It is well known that conventional demulsiiying agents may be used in a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oiland water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000 or 1 to 20,000 or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000 as in desalting practice, such an apparent insolubility in oil and water is not significant because said reagents undoubtedly have solubility within such concentrations. This same fact is true in regard to the material or materials employed as the demulsifying agent of my process.

In practicing the present process, the treating or demulsifying agent is used in the conventional way, well known to the art, described, for example, in Patent 2,626,929, dated January 2'7, 1953, Part 3, and reference is made thereto for a description of conventional procedures of demulsifying, including batch, continuous, and down-the-hole demulsification, the process essentially involving introducing a small amount of demulsifier into a large amount of emulsion with adequate admixture with or without the application of heat, and allowing the mixture to stratify.

As noted above, the products herein described may be used not only in diluted form, but also may be used admixed with some other chemical demulsifier. A mixture which illustrates such combination is the following:

The product of Example 11), 20%;

A cyclohexylamine salt of a napthalene monosulfonic acid, 24%;

An ammonium salt of a polypropylated napthalene monosulfonic acid, 24%;

A sodium salt of oil-soluble mahogany petroleum sulfonic acid, 12%;

A high-boiling aromatic petroleum solvent,

Isopropyl alcohol,

The above proportions are all weight percents.

The compounds herein described and particularly those adapted for breaking petroleum emulsions although having other uses as noted in my co-pending application, Serial No. 288,745, filed May 19, 1952, are derived from resins in which the bridge methylene group or a substituted methylene group.

Comparable amine-modified compounds serving all these various purposes are obtainable from another class of resins, i. e., those in which the phenolic nuclei are separated by a radical having at least a 3-carbon atoms chain and are obtained, not by the use of a single aldehyde but by the use of formaldehyde, in combination with a carbonyl compound selected from the class of aldehydes and ketones in which there is an alpha hydrogen atom available as in the case of acetaldehyde or acetone. Such resins almost invariably involve the use of a basic catalyst. Such bridge radicals between phenolic nuclei have either hydroxyl radicals, or carbonyl radicals, or both, and are invariably oxyalkylationsusceptible and may also enter into more complicated reactants with basic secondary amines. The bridge radical in the initial resin has distinct hydrophile character. Such resins or compounds which can be readily converted into such resins are described in the following patents.

Such analogous compounds are not included as part of the instant invention.

polypropylated between phenolic nuclei is a u U. S. Patents Nos. 2,191,802, dated February 27, 1940, to Novotny et al.; 2,448,664, dated September '7, 1948, to Fife et al.; 2,538,883, dated January 23, 1951, to Schrimpe; 2,538,884, dated January 23, 1951, to Schrimpe; 2,545,559, dated March 20, 1951, to Schrimpe; 2,750,389, dated October 9, 1951, to Schrimpe.

Having thus described my invention, what I claim as new and desire to secure by Letters Patent is:

1. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the products obtained in the process of condensing (a) an oxyalkylationsusceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenolaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated polyamine having at least one secondary amino group and having not over 82 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical; and (c) formaldehyde; said condensation reaction being conducted at a temperature sufiiciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible.

2. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the products obtained in the process of condensing (a) an oxyalkylation-susceptible, fusible, non-oxygenated organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity;- said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical below the pyrolytic point of the reactants and resultants of reaction; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the further proviso that the ratio of reactants be approximately 1, 2 and 2 respectively; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oXyalkylation-susceptible.

3. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the products obtained in the process of condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated, organic solvent-soluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any pri ture sufiiciently high to eliminate water and below the 'pyrolytic point of the reactants and resultants of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virture of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the ration of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation 26 product resulting from the process be heat-stable and oxyalkylation-susceptib1e.

4. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the products obtained in the process of condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic soivent soluble, water-insoluble, low-stage phenol-formaldehyde lfi'l ll having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said rosin being derived by reaction between a difuncticnal monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further provise that the polyamine be free from any primary amino radical, any substituted imidaaoline radiand any substituted tetrahydropyrimidine radical; and (0) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultant's of reaction, with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible.

5. A process for breaking petroleum emulsions of the water-in-oil type characterized by sub: jecting the emulsion to the action of a demulsifier including the products obtained in the process of condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solvent-soluble,

water-insoluble, low-stage phenohformaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difu'nctional only in regard to me'thylol-forming reactivity; said resin being derived by reaction between a dif-unctiona-l monohydric phenol and formaldehyde; said resin being formed in the substantial absence of tr'ifunctional phenols; said phenol being of the formula I on" in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 14 carbon atoms andsubstituted in the 2,4,6 position; (b) a basic hydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical; and formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of water and below 150 C., with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methylene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylationsusceptible.

6. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to the action of a demulsifier including the products obtained in the process of condensing (a) an oxyethylation-susceptible, fusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 12 carbon atoms and substituted in the para position; (b) a basic hydroxylated polyamine having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amine radical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical; and (0) formaldehyde; said condensation reaction being conducted at a temperature above the boiling point of water and below 150 C; with the proviso that the condensation reaction be conducted so as to produce a significant portion of the resultant in which each of the three reactants have contributed part of the ultimate molecule by virtue of a formaldehyde-derived methyl ene bridge connecting the amino nitrogen atom of reaction with a resin molecule; with the added proviso that the ratio of reactants be approximately 1, 2 and 2, respectively; with the further proviso that said procedure involve the use of a 28 solvent; and with the final proviso that the resinous condensation product resulting from the process be heat-stable and oxyalkylation-susceptible.

7. The process of claim 1 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufucient to produce an emulsion when said xylene solution is shaken vigorously with 1 .to 3 volumes of water.

8. The process of .claim 2 With the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the freebase, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

9. The process of claim 3 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

10. The process of claim 4 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, the salt of hydroxy acetic acid, in an equal of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

11. The process of claim 5 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufficient to produce an emulsion When said xylene solution is shaken vigorously with 1 to 3 volumes of Water.

12. The process of claim 6 with the proviso that the hydrophile properties of the product of the condensation reaction employed in the form of a member of the class consisting of (a) the anhydro base as is, (b) the free base, and (c) the salt of hydroxy acetic acid, in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with 1 to 3 volumes of water.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,931,557 Bruson Feb. 18, 1936 2,262,739 De Groote Nov. 11, 1941 2,290,154 Blair July 21, 1942 2,457,634 Bond et a1 Dec. 28, 1948 2,499,365 De Groote Mar. 7, 1950 2,499,368 De Groote Mar. 7, 1950 2,570,377 Revukas Oct. 9, 1951 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING THE PRODUCTS OBTAINED IN THE PROCESS OF CONDENSING (A) AN OXYALKYLATIONSUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOLALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOLFORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 